WO2021172879A1 - 리튬 금속 음극의 제조방법, 이에 의해 제조된 리튬 금속 음극 및 이를 포함하는 리튬-황 전지 - Google Patents

리튬 금속 음극의 제조방법, 이에 의해 제조된 리튬 금속 음극 및 이를 포함하는 리튬-황 전지 Download PDF

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WO2021172879A1
WO2021172879A1 PCT/KR2021/002345 KR2021002345W WO2021172879A1 WO 2021172879 A1 WO2021172879 A1 WO 2021172879A1 KR 2021002345 W KR2021002345 W KR 2021002345W WO 2021172879 A1 WO2021172879 A1 WO 2021172879A1
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lithium
lithium metal
negative electrode
sulfur
metal negative
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PCT/KR2021/002345
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English (en)
French (fr)
Korean (ko)
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정언호
이재길
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주식회사 엘지에너지솔루션
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Priority claimed from KR1020210024094A external-priority patent/KR20210109455A/ko
Application filed by 주식회사 엘지에너지솔루션 filed Critical 주식회사 엘지에너지솔루션
Priority to EP21761351.2A priority Critical patent/EP3996170B1/en
Priority to JP2022502963A priority patent/JP7309032B2/ja
Priority to CN202180004506.8A priority patent/CN114097110A/zh
Priority to US17/626,986 priority patent/US20220416221A1/en
Publication of WO2021172879A1 publication Critical patent/WO2021172879A1/ko

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for manufacturing a lithium metal negative electrode, a lithium metal negative electrode prepared thereby, and a lithium-sulfur battery comprising the same.
  • lithium secondary batteries As the application range of lithium secondary batteries is expanded to not only portable electronic devices but also electric vehicles (EVs) and electric storage systems (ESSs), the demand for lithium secondary batteries with high capacity, high energy density and long life is increasing. have.
  • EVs electric vehicles
  • ESSs electric storage systems
  • lithium-sulfur batteries use a sulfur-based material containing a sulfur-sulfur bond as a positive electrode active material, and lithium metal, a carbon-based material in which lithium ion insertion/deintercalation occurs, or lithium It is a battery system that uses silicon or tin, which forms an alloy with the anode, as an anode active material.
  • sulfur which is the main material of the cathode active material, has a low weight per atom, is easy to supply due to abundant resources, is inexpensive, has no toxicity, and is an environmentally friendly material.
  • the lithium-sulfur battery has a theoretical specific capacity of 1,675 mAh/g resulting from the conversion reaction of lithium ions and sulfur (S 8 +16Li + +16e - ⁇ 8Li 2 S) at the positive electrode, and the negative electrode It shows a theoretical energy density of 2,600 Wh/kg when lithium metal is used.
  • This is another cell system currently being studied (Ni-MH cell: 450 Wh/kg, Li-FeS cell: 480 Wh/kg, Li-MnO 2 cell: 1,000 Wh/kg, Na-S cell: 800 Wh/kg).
  • Ni-MH cell 450 Wh/kg
  • Li-FeS cell 480 Wh/kg
  • Li-MnO 2 cell 1,000 Wh/kg
  • Na-S cell 800 Wh/kg.
  • it since it has a very high value compared to the theoretical energy density of a lithium ion battery (250 Wh/kg), it is attracting attention as a high-capacity, eco-friendly and low-cost lithium secondary
  • a solid electrolyte interface layer (SEI layer), a type of passivation layer, is formed on the surface of the anode. . Since the solid electrolyte interfacial layer formed in this way suppresses a direct reaction between the electrolyte and the lithium metal, it is possible to secure a certain level of stability for the negative active material including lithium metal. was to be formed stably and uniformly.
  • the anode active material in a lithium-sulfur battery is lithium metal
  • the solid electrolyte interface layer is formed as described above, the electrochemical reaction of the battery continuously occurs on the surface of the lithium metal, so it is necessary to keep the solid electrolyte interface layer constant. is difficult
  • the solid electrolyte interfacial layer formed by the reaction of the electrolyte and lithium metal has weak mechanical strength, the structure collapses as the battery charging and discharging proceeds, resulting in a difference in local current density, resulting in a dendritic lithium dendrite on the lithium metal surface.
  • the lithium dendrite formed in this way causes an internal short circuit of the battery and inert lithium (dead lithium), which not only increases the physical and chemical instability of the lithium secondary battery, but also reduces the capacity of the battery and shortens the cycle life.
  • Lithium-sulfur batteries using lithium metal as an anode have not been commercialized due to the high instability of lithium metal and the problem of generation of lithium dendrites as described above.
  • Korean Patent Laid-Open No. 2016-0034183 discloses that a protective layer is formed with a polymer matrix capable of accumulating an electrolyte while protecting the anode on an anode active layer containing lithium metal or lithium alloy, thereby preventing loss of electrolyte and generation of dendrites. It is disclosed that it can be prevented.
  • Korean Patent Laid-Open No. 2016-0052351 discloses that the growth of lithium dendrites can be inhibited by including a lithium dendrite absorbent material in a polymer protective film formed on the surface of lithium metal, thereby improving the stability and lifespan characteristics of a lithium secondary battery. are doing
  • Jiangfeng Qian et al. and Korean Patent Application Laid-Open No. 2013-0079126 discloses lithium metal by increasing the lithium salt concentration or including a non-aqueous organic solvent including 1,3,5-trioxane, 1,3-dioxolane and a fluorine-based cyclic carbonate, respectively. It is disclosed that the characteristics of the battery can be improved.
  • Lithium metal electrode having a stable protective layer and lithium secondary battery including the same
  • the present inventors have conducted various studies to solve the above problem, and as a result, when lithium nitride powder is fixed to the surface of lithium metal through rolling to form a powdery lithium nitride protective layer, lithium dendrite growth is suppressed.
  • the present invention was completed by confirming that the capacity and lifespan of the lithium-sulfur battery can be improved by improving the lithium ion properties.
  • an object of the present invention is to provide a method for manufacturing a lithium metal negative electrode capable of forming a powdery lithium nitride protective layer having excellent properties on lithium metal.
  • Another object of the present invention is to provide a lithium metal anode manufactured according to the above manufacturing method and a lithium-sulfur battery including the same.
  • the lithium nitride powder may have an average particle diameter (D 50 ) of 0.1 to 100 ⁇ m.
  • the application process may be performed through spraying.
  • the rolling process may be performed by placing a lithium metal layer coated with lithium nitride powder between the rolling plates, applying heat or pressure, and then removing the rolled plate.
  • the rolling process may be performed under a temperature condition of room temperature (25 °C) to 120 °C.
  • the rolling process may be performed under a pressure condition of 0.1 to 980 kN.
  • the present invention is prepared by the above manufacturing method, the lithium metal layer comprising a lithium metal; And it provides a lithium metal negative electrode comprising a powdered lithium nitride protective layer fixed without a binder by rolling lithium nitride powder on at least one surface of the lithium metal layer.
  • the powdery lithium nitride protective layer may have a thickness of 0.1 to 100 ⁇ m.
  • the lithium metal negative electrode may have a surface resistance of 10 to 500 ⁇ .
  • the lithium ion conductivity of the powdery lithium nitride protective layer may be 0.0001 to 0.005 S/cm.
  • the present invention provides a lithium-sulfur battery including the lithium metal negative electrode.
  • the method for manufacturing a lithium metal negative electrode according to the present invention forms a powdery lithium nitride protective layer on the surface of lithium metal to suppress the formation of lithium dendrites and improve lithium ion conductivity of the negative electrode. It enables high capacity and long life.
  • Example 1 is a photograph showing the surface of the lithium metal negative electrode according to Example 1 and Comparative Example 1 ((a): Comparative Example 1, (b): Example 1).
  • FIG. 2 is a graph showing the results of evaluation of lifespan characteristics of lithium-sulfur batteries according to Example 2 and Comparative Example 2.
  • FIG. 2 is a graph showing the results of evaluation of lifespan characteristics of lithium-sulfur batteries according to Example 2 and Comparative Example 2.
  • Example 3 is a graph showing the evaluation results of the capacity characteristics of the lithium-sulfur battery according to Example 2.
  • composite refers to a material in which two or more materials are combined to form different phases physically and chemically while exhibiting more effective functions.
  • Lithium secondary batteries which were used in portable electronic devices and stayed in a limited market, are rapidly expanding to electric vehicle (EV) and energy storage system markets. is being requested
  • Lithium-sulfur batteries exhibit high theoretical discharge capacity and theoretical energy density among various secondary batteries, and lithium metal, which is mainly used as an anode active material, has a very small atomic weight (6.94 g/au) and density (0.534 g/cm 3 ). And it is easy to reduce the weight, so it is spotlighted as a next-generation battery.
  • lithium metal has high reactivity
  • a passivation film called a solid electrolyte interfacial layer is formed on the surface of the lithium metal due to spontaneous decomposition of the electrolyte.
  • the formation of such a solid electrolyte interfacial layer reduces the initial efficiency and capacity of the battery due to an irreversible lithium consumption reaction.
  • the solid electrolyte interfacial layer easily collapses during continuous charging and discharging, the current density on the lithium metal surface becomes non-uniform to form lithium dendrites and inert lithium, thereby reducing overall performance of the lithium-sulfur battery.
  • lithium polysulfide eluted from the positive electrode causes a side reaction with lithium metal, which causes lithium sulfide to adhere to the surface of the lithium metal, causing passivation of the electrode. It can be implemented up to about %, and as the cycle progresses, a problem occurs in that the decrease in capacity and lifespan is accelerated.
  • lithium nitride (Li 3 N) powder is used as an anode active material of lithium metal to suppress the formation of lithium dendrites in the lithium metal negative electrode to secure the effect of improving the capacity and lifespan characteristics of a lithium-sulfur battery including the same.
  • lithium nitride powder by using lithium nitride powder, it is possible to form a lithium nitride protective layer in a powder bed containing lithium nitride in the form of particles on the surface of the lithium metal.
  • a coating composition containing a polymer serving as a binder is applied when forming a lithium nitride protective layer on a lithium metal surface, or a chemical bonding method of reacting a lithium nitride precursor and a lithium metal is used.
  • the lithium nitride protective layer includes a polymer binder, etc.
  • a protective layer can be stably formed on the lithium metal surface, but there is a problem of battery performance degradation due to the resistance action of the polymer included in the protective layer when the battery is driven.
  • the lithium nitride protective layer is formed through the lithium nitride precursor, it is excellent in terms of thickness and loading amount, but reaction efficiency, economic efficiency, productivity, and the like may be reduced because a process of several steps is required.
  • a powdery lithium nitride protective layer is uniformly formed because a physical bond is formed between the lithium nitride powder and the lithium metal by applying the lithium nitride powder directly to the lithium metal surface and rolling it. Binding to metals is also very good.
  • the powdery lithium nitride protective layer thus formed can improve the stability of the lithium metal negative electrode and effectively suppress the formation of lithium dendrites, and improve the capacity and lifespan characteristics of a lithium-sulfur battery including the same. .
  • since lithium nitride in the form of particles exhibits lithium ion conductivity, the effect of improving the capacity characteristics of the lithium-sulfur battery including the lithium metal electrode according to the present invention is promoted.
  • the manufacturing method of the lithium metal negative electrode according to the present invention has the advantage that the process is very simple and easy to apply.
  • step (a) lithium nitride powder is applied on at least one surface of a lithium metal layer including lithium metal.
  • the lithium nitride powder may have an average particle diameter (D 50 ) of 0.1 to 100 ⁇ m.
  • D 50 is an index for defining a particle diameter distribution, which is generally referred to as a particle size distribution or a particle size distribution.
  • D 50 is defined as the particle diameter at the point where the volume is 50% by accumulating from the smallest particle size distribution, that is, the cumulative frequency of the volume distribution reaching 50%.
  • the average particle diameter of the lithium nitride powder may have a lower limit of 0.1 ⁇ m or more, 1 ⁇ m or more, or 10 ⁇ m or more, and an upper limit of 1 ⁇ m or less, 10 ⁇ m or less, or 100 ⁇ m or less.
  • the average particle diameter of the lithium nitride powder may be set by a combination of the lower limit and the upper limit. If the average particle diameter of the lithium nitride powder is less than the above range, an overvoltage occurs due to blockage of a passage through which lithium ions or electrolytes pass on the surface of the lithium metal layer, so that the intended effect cannot be obtained. Conversely, when the content of the average particle diameter of the lithium nitride powder exceeds the above range, the thickness of the lithium nitride protective layer may increase and the passage of lithium ions may increase, resulting in loss of energy density or shortening of lifespan of the battery.
  • the lithium metal layer may include a lithium metal thin film or lithium metal powder.
  • the application process may be performed by a commonly known method, for example, by using a method of spraying.
  • the application may be performed through a method of spraying lithium nitride powder.
  • step (b) the powder coated in step (a) is rolled to form a powdery lithium nitride protective layer on at least one surface of the lithium metal layer.
  • step (b) the rolling process applies heat, pressure, or a combination thereof to bond or fuse lithium nitride powder in particle form to the surface of lithium metal to fix it without a binder, thereby forming the lithium nitride protective layer in powder form. and forming on at least one surface of the metal layer.
  • the heating may be performed at room temperature (25 °C) to 120 °C, preferably at a temperature of 80 to 120 °C for 1 to 60 minutes.
  • the heating temperature and time may vary depending on process conditions. When the heating temperature is less than the above range, sufficient rolling is not made, so that the desired powdery lithium nitride protective layer cannot be formed. Conversely, when the heating temperature exceeds the above range, lithium metal may be melted.
  • the pressing in the rolling process of step (b) may be performed using a laminator or a pressing press (roll press).
  • the pressurization may be performed for 1 to 60 minutes under a pressure range of 0.1 to 980 kN, preferably 0.1 to 100 kN.
  • the pressure and time during the pressurization may vary depending on the material or process conditions.
  • step (b) When heat and pressure are simultaneously applied in the rolling process of step (b), it may be performed using a hot roll press or the like.
  • the lithium metal layer coated with the lithium nitride powder is placed between the rolling plates and using a thermocompression press machine.
  • the rolling process may be performed by heating or pressing.
  • the rolled plate preferably includes a chemically inert material.
  • the rolled plate may be a polymer film such as polyethylene, polyethylene terephthalate, or polypropylene, or a metal plate such as copper or a copper alloy. The rolled plate is removed after the rolling process.
  • a single powdery lithium nitride protective layer may be formed.
  • steps (a) and (b) are performed again to secondaryly form a powdery lithium A nitride protective layer can be formed, and by repeating steps (a) and (b) in this way, a powdery lithium nitride protective layer is laminated to form a powdery lithium nitride protective layer of a multilayer structure. . That is, the thickness and the laminated structure of the powdery lithium nitride protective layer can be easily controlled by repeating the process.
  • a lithium metal negative electrode including a lithium nitride protective layer in a uniform powder form can be easily obtained by applying and rolling lithium nitride powder to the surface of lithium metal to fix it without a binder.
  • the powdery lithium nitride protective layer prepared by the manufacturing method of the present invention has excellent uniformity to improve the stability of lithium metal, as well as to have a certain level of lithium ion conductivity including the powdery particle in the form of particles to improve capacity characteristics. effective. Accordingly, the performance of the lithium-sulfur battery can be improved.
  • the present invention provides a lithium metal negative electrode manufactured by the above manufacturing method.
  • the lithium metal negative electrode may include a lithium metal layer including lithium metal; and a powdery lithium nitride protective layer formed on at least one surface of the lithium metal layer.
  • the lithium metal layer may include a lithium metal thin film or lithium metal powder, or a lithium metal plate in which a lithium metal thin film is formed on at least one surface of the anode current collector.
  • the negative electrode current collector is for supporting the negative electrode active material layer, and is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, palladium, calcined carbon, a copper or stainless steel surface treated with carbon, nickel, silver, etc., an aluminum-cadmium alloy, etc. may be used.
  • the negative electrode current collector can form fine concavities and convexities on its surface to strengthen the bonding strength with the lithium metal thin film, which is an anode active material, and can take various forms such as films, sheets, foils, meshes, nets, porous bodies, foams, and nonwovens. Can be used.
  • a method of forming the lithium metal thin film is not particularly limited, and a method of forming a layer or a film commonly used in the art may be used. For example, a method such as pressing, coating, or vapor deposition may be used.
  • the powdery lithium nitride protective layer is formed according to the above-described manufacturing method, and may have a thickness in the range of 0.1 to 100 ⁇ m.
  • the thickness of the powdery lithium nitride protective layer may have a lower limit of 0.1 ⁇ m or more, 1 ⁇ m or more, or 10 ⁇ m or more, and an upper limit of 1 ⁇ m or less, 10 ⁇ m or less, or 100 ⁇ m or less.
  • the thickness of the powdery lithium nitride protective layer may be set by a combination of the lower limit value and the upper limit value. If the thickness of the powdery lithium nitride protective layer is less than the above range, there is a fear that the intended function as a protective layer may not be performed. can
  • the lithium ion conductivity of the powdery lithium nitride protective layer may be in the range of 0.0001 to 0.005 S/cm, preferably 0.001 to 0.002 S/cm. Since the lithium metal electrode according to the present invention includes a protective layer including powdery lithium nitride particles, it may exhibit superior lithium ion conductivity compared to a lithium metal electrode including a conventional lithium nitride protective layer.
  • the surface resistance of the lithium metal negative electrode having the powdery lithium nitride protective layer formed therein is 10 to 500 ⁇ , preferably 50 to 300 ⁇ , more preferably 100 to 250 ⁇ , and 1 to 240 hours. , preferably 24 to 120 hours, preferably no change in resistance for 36 to 48 hours. This is to prevent the continuous electrochemical reaction of the battery on the surface of the lithium metal unlike the conventional one, which means that the powdery lithium nitride protective layer is maintained in a stable state without reacting with the electrolyte.
  • the present invention provides a lithium-sulfur battery including the lithium metal negative electrode.
  • the lithium-sulfur battery includes a positive electrode; It includes a negative electrode and an electrolyte interposed therebetween, and includes the lithium metal negative electrode according to the present invention as the negative electrode.
  • the positive electrode may include a positive electrode current collector and a positive electrode active material layer coated on one or both surfaces of the positive electrode current collector.
  • the positive electrode current collector is for supporting the positive electrode active material, as described in the negative electrode current collector.
  • the positive electrode active material layer includes a positive electrode active material, and may further include a conductive material, a binder, and an additive.
  • the positive active material includes sulfur, and specifically, may include at least one selected from the group consisting of elemental sulfur (S 8 ) and sulfur compounds.
  • the positive active material may be inorganic sulfur.
  • the sulfur contained in the positive electrode active material since it does not have electrical conductivity alone, it is used in combination with a conductive material such as a carbon material. Accordingly, the sulfur is included in the form of a sulfur-carbon composite, and preferably, the cathode active material may be a sulfur-carbon composite.
  • the carbon included in the sulfur-carbon composite is a porous carbon material that provides a skeleton in which the sulfur can be uniformly and stably fixed, and compensates for the low electrical conductivity of sulfur so that the electrochemical reaction can proceed smoothly.
  • the porous carbon material may be generally prepared by carbonizing precursors of various carbon materials.
  • the porous carbon material includes non-uniform pores therein, and the average diameter of the pores is in the range of 1 to 200 nm, and the porosity or porosity may be in the range of 10 to 90% of the total volume of the porous carbon material. If the average diameter of the pores is less than the above range, impregnation of sulfur is impossible because the pore size is only at the molecular level. Not desirable.
  • the shape of the porous carbon material is spherical, rod-shaped, needle-shaped, plate-shaped, tube-shaped or bulk-shaped, as long as it is conventionally used in lithium-sulfur batteries, and may be used without limitation.
  • the porous carbon material may have a porous structure or a high specific surface area, as long as it is commonly used in the art.
  • the porous carbon material may include graphite; graphene; carbon black such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; carbon nanotubes (CNTs) such as single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs); carbon fibers such as graphite nanofibers (GNF), carbon nanofibers (CNF), and activated carbon fibers (ACF); It may be at least one selected from the group consisting of graphite and activated carbon such as natural graphite, artificial graphite, and expanded graphite, but is not limited thereto.
  • the porous carbon material may be a carbon nanotube.
  • the sulfur-carbon composite may include sulfur in an amount of 60 to 90 parts by weight, preferably 65 to 85 parts by weight, and more preferably 70 to 80 parts by weight, based on 100 parts by weight of the sulfur-carbon composite.
  • sulfur content is less than the above-mentioned range, the specific surface area increases as the content of the porous carbon material in the sulfur-carbon composite is relatively increased, so that the binder content increases when the positive electrode is manufactured.
  • An increase in the amount of the binder used may eventually increase the sheet resistance of the positive electrode and act as an insulator to prevent electron pass, thereby degrading the performance of the battery.
  • the sulfur which cannot be combined with the porous carbon material, aggregates with each other or re-elutes to the surface of the porous carbon material, making it difficult to receive electrons and not participating in the electrochemical reaction of the battery. Capacity loss may occur.
  • the sulfur is located on at least one of the inner and outer surfaces of the aforementioned porous carbon material, wherein less than 100%, preferably 1 to 95% of the total inner and outer surfaces of the porous carbon material , more preferably 60 to 90%.
  • the sulfur is present on the inner and outer surfaces of the porous carbon material within the above range, the maximum effect may be exhibited in terms of electron transport area and wettability with the electrolyte.
  • sulfur is thinly and evenly impregnated on the inner and outer surfaces of the porous carbon material in the above range, it is possible to increase the electron transport contact area in the charge/discharge process.
  • the sulfur is located in 100% of the entire inner and outer surface of the porous carbon material, the carbon material is completely covered with sulfur, so that the wettability to the electrolyte is reduced and the contact with the conductive material included in the electrode is lowered to prevent electron transfer. They cannot participate in the electrochemical reaction.
  • the method for preparing the sulfur-carbon composite is not particularly limited in the present invention, and a method commonly used in the art may be used. As an example, a method of simply mixing the sulfur and the porous carbon material and then heat-treating the compound may be used.
  • the positive active material may further include one or more additives selected from a transition metal element, a group IIIA element, a group IVA element, a sulfur compound of these elements, and an alloy of these elements and sulfur in addition to the composition described above.
  • transition metal element examples include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Os, Ir, Pt, Au or Hg and the like are included, and the group IIIA elements include Al, Ga, In, Ti, and the like, and the group IVA elements include Ge, Sn, Pb, and the like.
  • the positive active material may be included in an amount of 40 to 95% by weight, preferably 50 to 90% by weight, more preferably 60 to 85% by weight based on 100% by weight of the total weight of the positive active material layer constituting the positive electrode.
  • content of the positive electrode active material is less than the above range, it is difficult to sufficiently exhibit the electrochemical reaction of the positive electrode, and on the contrary, when it exceeds the above range, the content of the conductive material and the binder to be described later is relatively insufficient, and the resistance of the positive electrode increases, There is a problem in that the physical properties of the anode are deteriorated.
  • the positive electrode active material layer may optionally further include a conductive material for allowing electrons to smoothly move within the positive electrode (specifically, the positive electrode active material) and a binder for well adhering the positive electrode active material to the current collector.
  • the conductive material electrically connects the electrolyte and the positive electrode active material to serve as a path for electrons to move from the current collector to the positive electrode active material, and may be used without limitation as long as it has conductivity.
  • the conductive material may include graphite such as natural graphite and artificial graphite; carbon black such as Super-P (Super-P), Denka Black, Acetylene Black, Ketjen Black, Channel Black, Furnace Black, Lamp Black, and Summer Black; carbon derivatives such as carbon nanotubes and fullerenes; conductive fibers such as carbon fibers and metal fibers; carbon fluoride; Metal powders, such as aluminum and nickel powder, or conductive polymers, such as polyaniline, polythiophene, polyacetylene, polypyrrole, can be used individually or in mixture.
  • graphite such as natural graphite and artificial graphite
  • carbon black such as Super-P (Super-P), Denka Black, Acetylene Black, Ketjen Black, Channel Black, Furnace Black, Lamp Black, and Summer Black
  • carbon derivatives such as carbon nanotubes and fullerenes
  • conductive fibers such as carbon fibers and metal fibers
  • carbon fluoride carbon fluoride
  • the conductive material may be included in an amount of 0.01 to 30% by weight based on 100% by weight of the total of the positive active material layer constituting the positive electrode.
  • the content of the conductive material is less than the above range, electron transfer between the positive active material and the current collector is not easy, so that the voltage and capacity decrease.
  • the amount exceeds the above range the ratio of the positive electrode active material is relatively decreased, so that the total energy (charge amount) of the battery may decrease, so it is preferable to determine an appropriate content within the above-described range.
  • the binder maintains the positive electrode active material on the positive electrode current collector and organically connects the positive electrode active materials to increase the binding force between them, and any binder known in the art may be used.
  • the binder may include a fluororesin-based binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE); a rubber-based binder including styrene-butadiene rubber (SBR), acrylonitrile-butydiene rubber, and styrene-isoprene rubber; Cellulose binders including carboxyl methyl cellulose (CMC), starch, hydroxypropyl cellulose, and regenerated cellulose; polyalcohol-based binders; Polyolefin-based binders including polyethylene and polypropylene; polyimide-based binders; polyester-based binders; and a silane-based binder; one selected from the group consisting of, a mixture or copolymer of two or more may be used.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • the content of the binder may be 0.5 to 30% by weight based on 100% by weight of the total of the positive active material layer constituting the positive electrode. If the content of the binder is less than the above range, the physical properties of the positive electrode may be deteriorated, and the positive electrode active material and the conductive material may fall off. It is preferable to determine the appropriate content within the above-mentioned range.
  • the method for manufacturing the positive electrode is not particularly limited, and a method known by those skilled in the art or various methods for modifying it may be used.
  • the positive electrode may be prepared by preparing a positive electrode slurry composition including the composition as described above and then applying it to at least one surface of the positive electrode current collector.
  • the positive electrode slurry composition includes the positive electrode active material, the conductive material, and the binder as described above, and may further include a solvent.
  • the solvent a solvent capable of uniformly dispersing the positive electrode active material, the conductive material, and the binder is used.
  • water is most preferable as an aqueous solvent, and in this case, the water may be distilled water or deionzied water.
  • the present invention is not necessarily limited thereto, and if necessary, a lower alcohol that can be easily mixed with water may be used. Examples of the lower alcohol include methanol, ethanol, propanol, isopropanol and butanol, and preferably, these may be used by mixing with water.
  • the content of the solvent may be contained at a level having a concentration capable of facilitating coating, and the specific content varies depending on the application method and apparatus.
  • the positive electrode slurry composition may additionally include a material commonly used for the purpose of improving its function in the relevant technical field, if necessary.
  • a viscosity modifier for example, a viscosity modifier, a fluidizing agent, a filler, etc. are mentioned.
  • the method of applying the positive electrode slurry composition is not particularly limited in the present invention, and for example, methods such as doctor blade, die casting, comma coating, screen printing, etc. can
  • the positive electrode slurry may be applied on the positive electrode current collector by a pressing or lamination method.
  • a drying process for removing the solvent may be performed.
  • the drying process is performed at a temperature and time at a level sufficient to remove the solvent, and the conditions may vary depending on the type of the solvent, so the present invention is not particularly limited.
  • drying by hot air, hot air, low humidity air, vacuum drying, (far) infrared rays and a drying method by irradiation with an electron beam, etc. are mentioned.
  • the drying rate is usually adjusted to remove the solvent as quickly as possible within a speed range such that the positive electrode active material layer is not cracked or the positive electrode active material layer is not peeled off from the positive electrode current collector due to stress concentration.
  • the density of the positive electrode active material in the positive electrode may be increased by pressing the current collector after drying.
  • Methods, such as a die press and roll press, are mentioned as a press method.
  • the porosity of the positive electrode specifically, the positive electrode active material layer, prepared by the composition and manufacturing method as described above may be 50 to 80%, preferably 60 to 75%.
  • the porosity of the positive electrode is less than 50%, the filling degree of the positive electrode slurry composition including the positive electrode active material, the conductive material and the binder is excessively high, so that sufficient electrolyte to exhibit ionic and/or electrical conduction between the positive electrode active materials is provided. Since it cannot be maintained, the output characteristics or cycle characteristics of the battery may be deteriorated, and there is a problem in that the overvoltage and the discharge capacity of the battery are severely reduced.
  • the sulfur loading in the positive electrode according to the present invention that is, the mass of sulfur per unit area of the positive electrode active material layer in the positive electrode may be 0.5 to 15 mg/cm 2 , preferably 1 to 10 mg/cm 2 .
  • the negative electrode is as described above.
  • the electrolyte contains lithium ions, and is to cause an electrochemical oxidation or reduction reaction in the positive electrode and the negative electrode through this.
  • the electrolyte may be a non-aqueous electrolyte or a solid electrolyte that does not react with lithium metal, but is preferably a non-aqueous electrolyte, and includes an electrolyte salt and an organic solvent.
  • the electrolyte salt contained in the non-aqueous electrolyte is a lithium salt.
  • the lithium salt may be used without limitation as long as it is commonly used in an electrolyte for a lithium secondary battery.
  • LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, ( CF 3 SO 2 ) 2 NLi, LiN(SO 2 F) 2 , lithium chloroborane, lithium lower aliphatic carboxylate, lithium 4-phenyl borate, lithium imide, or the like may be used.
  • the concentration of the lithium salt varies from 0.2 to 2 M, depending on several factors such as the exact composition of the electrolyte solvent mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and preconditioning of the cell, the operating temperature and other factors known in the art of lithium batteries; Specifically, it may be 0.4 to 2 M, more specifically 0.4 to 1.7 M. If the concentration of the lithium salt is less than 0.2 M, the conductivity of the electrolyte may be lowered, and thus the electrolyte performance may be deteriorated.
  • organic solvent included in the non-aqueous electrolyte those commonly used in electrolytes for lithium secondary batteries may be used without limitation, for example, ethers, esters, amides, linear carbonates, cyclic carbonates, etc. individually or in a mixture of two or more can be used by Among them, an ether-based compound may be typically included.
  • the ether-based compound may include an acyclic ether and a cyclic ether.
  • the acyclic ether includes dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, ethylpropyl ether, dimethoxyethane, diethoxyethane, ethylene glycol ethylmethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methylethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, At least one selected from the group consisting of tetraethylene glycol methylethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, and polyethylene glycol methylethyl ether may be used, but the present invention is not limited thereto.
  • the cyclic ether is 1,3-dioxolane, 4,5-dimethyl-dioxolane, 4,5-diethyl-dioxolane, 4-methyl-1,3-dioxolane, 4-ethyl-1, 3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, 2-methyl-1,3 -dioxolane, 2-vinyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2-methoxy-1,3-dioxolane, 2-ethyl-2-methyl-1, 3-dioxolane, tetrahydropyran, 1,4-dioxane, 1,2-dimethoxy benzene, 1,3-dimethoxy benz
  • Esters in the organic solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ - Any one selected from the group consisting of valerolactone and ⁇ -caprolactone or a mixture of two or more thereof may be used, but the present invention is not limited thereto.
  • linear carbonate compound examples include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate or among them
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • methylpropyl carbonate methylpropyl carbonate
  • ethylpropyl carbonate methylpropyl carbonate
  • ethylpropyl carbonate methylpropyl carbonate
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate , 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and any one selected from the group consisting of halides thereof, or a mixture of two or more thereof.
  • halides include, but are not limited to, fluoroethylene carbonate (FEC).
  • the electrolyte may further include nitric acid or a nitrite-based compound as an additive in addition to the above-described electrolyte salt and the organic solvent.
  • the nitric acid or nitrite-based compound has the effect of forming a stable film on the lithium metal electrode, which is the negative electrode, and improving the charging and discharging efficiency.
  • the nitric acid or nitrite-based compound is not particularly limited in the present invention, but lithium nitrate (LiNO 3 ), potassium nitrate (KNO 3 ), cesium nitrate (CsNO 3 ), barium nitrate (Ba(NO 3 ) 2 ), ammonium nitrate inorganic nitric acid or nitrite compounds such as (NH 4 NO 3 ), lithium nitrite (LiNO 2 ), potassium nitrite (KNO 2 ), cesium nitrite (CsNO 2 ), and ammonium nitrite (NH 4 NO 2 ); Organic nitric acids such as methyl nitrate, dialkyl imidazolium nitrate, guanidine nitrate, imidazolium nitrate, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, and oc
  • the injection of the electrolyte may be performed at an appropriate stage in the manufacturing process of the electrochemical device according to the manufacturing process of the final product and required physical properties. That is, it may be applied before assembling the electrochemical device or in the final stage of assembling the electrochemical device.
  • a separator may be additionally included between the anode and the cathode.
  • the separator separates or insulates the positive electrode and the negative electrode from each other and enables lithium ion transport between the positive electrode and the negative electrode, and may be made of a porous non-conductive or insulating material.
  • the separator may be used without any particular limitation as long as it is used as a separator in a lithium-sulfur battery.
  • the separator may be an independent member such as a film, or may be a coating layer added to the positive electrode and/or the negative electrode.
  • the electrolyte has low resistance to ion movement and has excellent moisture content to the electrolyte.
  • the separator may be made of a porous substrate.
  • the porous substrate can be used as long as it is a porous substrate typically used in lithium-sulfur batteries, and a porous polymer film can be used alone or by laminating them, for example, A nonwoven fabric or a polyolefin-based porous membrane made of a melting point glass fiber, polyethylene terephthalate fiber, or the like may be used, but is not limited thereto.
  • the material of the porous substrate is not particularly limited in the present invention, and any porous substrate commonly used in lithium-sulfur batteries may be used.
  • the porous substrate may include a polyolefin such as polyethylene and polypropylene, a polyester such as polyethyleneterephthalate, and a polybutyleneterephthalate, and a polyamide.
  • polyamide polyacetal, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylenesulfide ( polyphenylenesulfide, polyethylenenaphthalate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, cellulose, nylon (nylon), polyparaphenylene benzobisoxazole (poly(p-phenylene benzobisoxazole) and polyarylate (polyarylate) may include at least one material selected from the group consisting of.
  • the thickness of the porous substrate is not particularly limited, but may be 1 to 100 ⁇ m, preferably 5 to 50 ⁇ m. Although the thickness range of the porous substrate is not limited to the above range, when the thickness is excessively thinner than the above-described lower limit, mechanical properties are lowered and the separator may be easily damaged during use of the battery.
  • the average diameter and pore size of the pores present in the porous substrate are also not particularly limited, but may be 0.001 to 50 ⁇ m and 10 to 95%, respectively.
  • the lithium secondary battery according to the present invention in addition to the general process of winding, lamination, stack, and folding processes of a separator and an electrode are possible.
  • the shape of the lithium secondary battery is not particularly limited and may have various shapes such as a cylindrical shape, a stacked type, and a coin type.
  • the present invention provides a battery module including the lithium-sulfur battery as a unit battery.
  • the battery module may be used as a power source for medium to large devices requiring high temperature stability, long cycle characteristics, and high capacity characteristics.
  • Examples of the medium-to-large device include a power tool that is powered by an omniscient motor; electric vehicles, including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooter); electric golf carts; and a power storage system, but is not limited thereto.
  • electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like
  • electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooter)
  • E-scooter electric bicycles
  • electric scooters E-scooter
  • electric golf carts and a power storage system, but is not limited thereto.
  • Lithium nitride (manufactured by Sigma-Aldrich Co.) was pulverized to prepare lithium nitride powder having an average particle diameter of 1 ⁇ m.
  • a positive electrode was prepared by coating the prepared positive electrode slurry composition on an aluminum current collector having a thickness of 20 ⁇ m, drying it at 100° C. for 12 hours, and pressing with a roll press device. At this time, the loading amount of the positive electrode active material was 5.6 mAh/cm 2 or less, and the porosity of the positive electrode was 68%.
  • the prepared positive electrode and the lithium metal negative electrode prepared in Example 1 were positioned to face each other, and a polyethylene separator having a thickness of 16 ⁇ m and a porosity of 45% was interposed therebetween, and 70 ⁇ l of the electrolyte was injected to form a lithium-sulfur battery. prepared.
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • LiNO 3 lithium nitrate
  • a lithium metal negative electrode was prepared using a lithium metal thin film having a thickness of 45 ⁇ m without a lithium nitride protective layer coated thereon.
  • a lithium-sulfur battery was prepared in the same manner as in Example 2, except that the lithium metal negative electrode of Comparative Example 1 was used instead of the lithium metal negative electrode of Example 1.
  • a lithium metal thin film having a thickness of 45 ⁇ m was prepared.
  • a lithium-sulfur battery was prepared in the same manner as in Example 2, except that the lithium metal negative electrode of Comparative Example 3 was used instead of the lithium metal negative electrode of Example 1.
  • Example 1 The surface of the lithium metal negative electrode prepared in Example 1 and Comparative Example 1 was visually evaluated. The results obtained at this time are shown in FIG. 1 .
  • the lithium metal negative electrode (b) according to Example 1 protects lithium nitride including lithium nitride powder on the surface because lithium nitride powder can be observed compared to Comparative Example 1 (a). It can be seen that the layers are included.
  • the battery of Example 2 has a higher capacity than the battery of Comparative Example 2 and at the same time has an excellent capacity retention rate during the charge/discharge cycle.
  • the lithium-sulfur battery of the present invention includes a lithium metal electrode including a lithium nitride protective layer, thereby improving the capacity and lifespan characteristics of the lithium-sulfur battery.
PCT/KR2021/002345 2020-02-27 2021-02-25 리튬 금속 음극의 제조방법, 이에 의해 제조된 리튬 금속 음극 및 이를 포함하는 리튬-황 전지 WO2021172879A1 (ko)

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EP21761351.2A EP3996170B1 (en) 2020-02-27 2021-02-25 Method for manufacturing lithium metal negative electrode, lithium metal negative electrode manufactured thereby, and lithium-sulfur battery comprising same
JP2022502963A JP7309032B2 (ja) 2020-02-27 2021-02-25 リチウム金属負極の製造方法、これによって製造されたリチウム金属負極及びこれを含むリチウム‐硫黄電池
CN202180004506.8A CN114097110A (zh) 2020-02-27 2021-02-25 制造锂金属负极的方法、由此方法制造的锂金属负极以及包含所述锂金属负极的锂硫电池
US17/626,986 US20220416221A1 (en) 2020-02-27 2021-02-25 Method for manufacturing lithium metal negative electrode, lithium metal negative electrode manufactured thereby, and lithium-sulfur battery comprising same

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